JPS59104348A - Spherical or semispherical tetrakis (3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionyloxymethyl)methane and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain the titled spherical or semispherical compound having a novel gamma crystal structure and a low melting point, by dropping a melt of the aimed compound onto the surface of a solid or water or extruding the melt in an inert gas or water in the form of drops, and solidifying the extruded drops. CONSTITUTION:A melt of tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl] methane expressed by the formula is dropped onto the surface of a smooth solid, e.g. a metallic plate, or the surface of the water or extruded into an inert gas or water in the form of drops, cooled and solidified to give the aimed spherical or semispherical compound expressed by the formula having gamma crystal structure. The compound expressed by the formula is used as an antioxidant for polyolefin, etc., but powder thereof having <=100mu particle diameter is not easily handled in the aspects of automatic measurement, supply, transportation, storage, etc. However, the above-mentioned compound, expressed by the formula, and having the novel gamma crystal structure has a remarkably low melting point (60-70 deg.C lower than that of the conventional compound), and uniform dispersion by melting is easily obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides tetrakis[:3-(3,5-di[-butyl-4-hydroxyphenyl)propionyloxymethylcomethane] having a spherical or hemispherical T crystal structure and a method for producing the same. Regarding.

Tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethylcomethane represented by the following formula (I) / -C4Hg] is a polyolefin, polyvinyl chloride, polyester, polystyrene, ABS resin. effect, polyurethane,
It is widely used as an antioxidant for polyacetal, vegetable oil, mineral oil, etc., but the compound generally has a particle size of 10
It is commercially available in powder form with a size of 0 μ or less, so it easily scatters.
Poor fluidity and poor working environment due to fine powder.
It has various drawbacks, such as being blocked during transportation and storage, which makes it difficult to measure and supply. In addition, when compound (1) is used for thermoplastic materials whose processing temperature is limited for practical reasons, such as polyvinyl chloride, polypropylene, or acrylonitrile-cyclodiene copolymer, it can be melted and mixed easily and uniformly. A material with a low melting point that is easy to melt is desired.

The purpose of the present invention is to form the compound (1) into a spherical or hemispherical form, which is the most ideal form, in order to improve the above-mentioned drawbacks and facilitate automatic measurement, supplyability, transportation, storage, and handling workability. At the same time, the aim is to lower the melting point so that it can be mixed more uniformly than in practical use, and to provide a compound (1) that has a form and a low melting point that have not been found heretofore.

Conventionally, methods for commercializing compound (1) include, for example, 3
-(3,5-di[-butyl-4-hydroxyphenyl)methyl propionate (a) and pentaerythritol (
A method of cooling a hot butane solution of the reaction product with bl, filtering the resulting solid, and washing and drying the solid with cold hexane - (Japanese Patent Publication No. 18617/1973), 95 Chitsu Probanol A method of recrystallizing with heptane, washing and drying with water (Japanese Patent Publication No. 42-19083), and a method of recrystallizing the reaction product with ethanol (Japanese Patent Publication No. 49-1983)
There are methods such as
No. 341 discloses a method of recrystallizing a candy-like substance containing compound (1) using inbutanol.

However, in all of these methods, white microcrystals are simply obtained by a recrystallization method, and no technique for obtaining a desirable form of compound f1+ for practical use is disclosed.

On the other hand, as a method for forming compound (1) into a good form, the above-mentioned raw materials (a) and (b) are reacted in the presence of compound (2) represented by the following general formula. A method of forming a molecular adduct by adding an alcohol having the property of forming a molecular adduct with the product, and then recrystallizing it in methanol or/and ethanol to obtain fine particles with good flowability. (JP-A-56-99444, JP-A-56-139
438).

However, such a method requires a large amount of expensive and dangerous solvent to handle, the purification process itself is extremely complicated, and the resulting product has a high melting point, which is required. It has not yet been fully titrated to meet industry needs. The latter document also describes a T-crystal product with a low melting point, but it merely states that it is glass-like and requires a pulverization process.

In view of the above circumstances, the present inventor conducted intensive research on a method of making compound (1) spherical or hemispherical and easily obtaining it as a T-structure having a low melting point. It is effective to drop 1) onto a smooth solid surface, such as a metal plate, on a water surface, or into an inert gas such as air or nitrogen, and cool and solidify it. ) It was discovered that the compound (1) having a T structure having a melting point 60 to 70° C. lower can be easily obtained in a good yield, leading to the completion of the present invention.

The liquid having the T structure represented by the above formula (1) and having a spherical or hemispherical shape was first produced by the present inventor, and can be produced by the following method.

(A) A method in which a melt of compound (1) is dropped onto a smooth solid surface, and is cooled and solidified on the surface.

Concave A method in which the molten compound (1) is dropped onto the water surface or discharged dropwise into the water, and then cooled and solidified in the water.

(C) A method in which the melted compound (1) is discharged dropwise into an inert gas, and is cooled and solidified in the gas.

The above methods will be explained in detail below.

In method 4, any material that can be used to form a smooth solid surface can be used without any particular restriction as long as the surface can be made smooth, such as metal plates such as aluminum, copper, iron, and stainless steel, silicon, etc. paper-like structures, such as paperboard, coated with a release agent to improve the releasability of its surface;
Plastic plates such as styrene, Teflon, and polypropylene are exemplified, but they have good thermal conductivity, have a cooling effect when the molten compound (1) is dropped, and have a good releasability of the cooled solidified material from the solid surface. In this respect, a metal plate is particularly preferred, and an aluminum plate, an aluminum plate with an alumite surface treatment, and a stainless steel plate are particularly preferred.

Of course, the surfaces of these solids need to be smooth so that the cooled and solidified material can be easily peeled off.

In implementing this method, a solid surface (solid plate)
A compound (1
) is dropped in a fixed amount at a time, the dropped material is cooled and solidified on the solid surface, and then it is peeled off from the solid surface and collected.

In this case, it is practically preferable to make either the nozzle or the surface of the same body mobile while the other is fixed, and particularly preferable is a method in which the melt of compound (1) is dripped onto a moving solid plate.

The temperature of the solid surface that receives the molten compound (1) is usually 5
-40°C, preferably 10-30°C.

If the temperature of the solid surface increases as the melt drips, it is necessary to cool it at any location and by any method to maintain the specified temperature. For example, by blowing cold air onto the solid surface. A method such as blowing is employed. In this case, in order to avoid dew condensation on the solid surface, the temperature is preferably higher than the dew point of the atmosphere.

There are two methods: one method is to drop drops onto the water surface from a nozzle installed at a predetermined position, and the other method is to discharge droplets into the water from a nozzle installed underwater, but the two methods are simply different in the method of dropping. There is no difference. If the water temperature is below 5°C, the resulting product will easily become brittle, and if the water temperature is higher than 25°C, the solidification rate will be slow and the product will tend to have a flat shape. In addition, if a small amount of surfactant is dissolved, it will be easier to disperse the solidified material during the cooling and assimilation process of the molten material.
Any surfactant having the following properties may be used, and a low-temperature one is preferably used. Specifically, a nonionic surfactant such as Emulgen pp-150 (Kao Atlas Co., Ltd.) has an aqueous solution concentration of 0005 to 0005. It is used so that the weight ratio is 0°2.

Note that while the melt is being dropped onto the water surface or being discharged dropwise into the water, it is desirable to maintain a suitable flow so that the water surface does not ripple so that the water surface is constantly moving.

The solidified product cooled and solidified in water is spherical or hemispherical, separated from the water, and dried to form the final product.

In the method (C) in which the molten compound (1) is discharged dropwise into an inert gas and cooled and solidified, the inert gas is air, nitrogen, etc., and usually air is used. That is, the molten material is dropped dropwise from a nozzle held at a predetermined height into the airflow inside the tower, and is cooled and solidified in the process until it reaches the bottom of the tower. The temperature of the gas in this case is the same as the temperature of the solid surface in the above-mentioned (Al method).The product thus obtained has a spherical or hemispherical shape, and it is easy to collect it.

The height of the tower used in method fc) is 5 to 2' or, usually 10 to 20 m, and if the tower is sufficiently cylindrical, it is sufficient to receive the fallen material in a flat plate-shaped tank. However, if the height of the tower is insufficient, the cooling of the fallen objects will be insufficient, so the
It is preferable to receive it in a tank containing water of 'C. In this case, the receipt.

The diameter of the product obtained in any of the above methods (Al, (B) and (C1) is adjusted by the diameter and shape of the nozzle used for dropping or discharging in droplets, and the dropping or discharging pressure, but usually The diameter of the product thus obtained is 0.1 to 10 mm, preferably 0.3 to 4 mm.

As a result of measuring the melting point of the thus obtained product of the present invention using a differential thermal analyzer, it was found to be 49°C, which is higher than that of conventional commercially available compounds (
1) was found to be lower than that in the range of 110 to 119°C in the same measurement, and the crystal structure of the product was measured by the X-ray diffraction spectrum using the 9 powder method. It was confirmed that the commercially available compound (1) was an α crystal, a β crystal, or a mixed crystal of α and β, whereas it was a T crystal.

In addition, the bulk specific gravity of the product obtained by the present invention was measured to be 9/l at 0°6, indicating that it is an extremely excellent granular material and has appropriate hardness, e.g.
It has a hardness of 0 y to 800 F.

The uninvented compound (1), which has a T structure and is spherical or hemispherical, solves the conventional problems in automatic weighing, supply, transportation, storage, and handling, and also has a remarkable melting point. It also has the feature of low temperature, and can significantly lower the temperature of mixing equipment such as rolls or Banbury mixers to uniformly disperse objects with low melting points or low softening points. can.

Particularly when applied to polyvinyl chloride, polypropylene, or acrylonitrile-butadiene copolymer, etc., where temperature is restricted during mixing, uniform dispersion by melting can be easily obtained.

In addition, when applied to vegetable oils and mineral oils, current commercially available products require the addition of a solution prepared in advance using an appropriate solvent, and high temperature heating is required for mixing, which can lead to deterioration of the oil. However, since the product of the present invention melts at a low temperature, it is easy to uniformly disperse it. It can be preferably used for corn oil, camellia oil, spindle oil, etc. where the mixing temperature is limited.

Hereinafter, the present invention will be explained by examples.

Example A commercially available compound (1) having a melting point of 113°C and a β-crystal is melted by heating and held in a nitrogen gas atmosphere at 145 to 160°C,
A 20°C aluminum plate (
The surface was alumite-treated and the back surface was removed by contacting it with a cloth moistened with water (4a) to remove heat), and it solidified in 15 seconds, and the solidified product was collected by cooling on the plate. The product thus obtained is transparent and spherical with a diameter of 2 to 3 mm, has a melting point with an endothermic peak reaching its maximum at 49°C according to differential thermal analysis, and exhibits a T structure according to X-ray diffraction. In addition, the particles had a bulk specific gravity of 0°6/l, a hardness under a load of 600, and an angle of repose of 30°, and had sufficient hardness and flowability for practical use.

Example 2 A commercially available compound (1) having a melting point of 113 to 120°C and a mixed crystal of α and β was melted by heating, and the mixture was maintained at a pressure of 0°5 Kti/crh2 in a nitrogen gas atmosphere at 155 to 165°C, and then passed through a number of dropping nozzles. Height 1 from metered injection device with (inner diameter 1.)
The mixture was placed in a tower through which 0% air at 20°C was passed, but it solidified in just 5 seconds. The product thus obtained has a diameter of 0°5.
~1°2mm spherical shape, melting point according to differential thermal analysis is 4
9℃, and X-ray diffraction shows pr structure, bulk specific gravity 0.6
2KP/l! The particles had a repose angle of 28°, sufficient hardness for practical use, and excellent flowability.

Example 3 A commercially available compound (1) with a melting point of 120°C and α crystal was melted by heating, maintained at 150 to 160°C in a nitrogen gas atmosphere, and quantitatively injected using a large number of dropping nozzles (inner diameter 2 to b■). The flow is supported by a fixed amount from the device at a certain depth and speed. It solidified within 5 seconds after dropping, and the solidified material settled in running water. Collect this and drain the water.
After air drying, a spherical product with a diameter of 2-4 rrLwn was obtained. The thus obtained product was measured in the same manner as in Example 1, and was found to have a melting point of 49°C, a T structure, a bulk specific gravity of 0662 mm/l, and a hardness of 5.
The particles had practically sufficient hardness with a load of 0.00 and an angle of repose of 30° and excellent flowability.

Example 4 Using the same apparatus and operation as in Example 3, a melt of the same commercially available compound (1) l surfactant Emulgen 9 was prepared.
05 (manufactured by Kao Atlas Co., Ltd., nonionic type) When dropped onto the surface of running water at 20°C in which 0.1% by weight had been dissolved, it solidified in 5 seconds. The product thus obtained has a spherical shape, with a diameter of 2~
It was 4 mm thick, had a melting point of 49° C., had a T structure, had sufficient hardness for practical use, and had excellent flowability.

Example 5 Using the same equipment and operation as in Example 1, a melt of the same commercially available compound (1) was dropped onto the surface of a moving silicon release paper at 20°C, and it solidified in 30 seconds. The product thus obtained had a hemispherical shape with a diameter of 2 to 3 mm, a melting point of 49° C., a T structure, and sufficient hardness for practical use and excellent flowability.

Procedural amendment (spontaneous) 6゜(1) January 1, 1981 Chugai Indication 1982 Patent Application No. 213055 2 Name of the invention Spherical or hemispherical tetrakis [-(3,5-sheet
-Archilu 1-4-hydroxyphenyl)flopionyloxymethyl]methane and its manufacturing method 3 Relationship with Jl'l name subject to amendment Patent applicant Fuchi7゜:= Address 5-15 Kitahama, Higashi-ku, Osaka Address: Contents of amendment in the Detailed Description of the Invention column of the specification In the 5th line of page 10 of the specification, [-Low-temperature property-1] is corrected to read 'low foaming property'.

that's all

Claims (5)

[Claims] (1) Tetrakis[:3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethylcomethane] having a spherical or hemispherical gamma crystal structure. (2) Drop the melt of tetrakis[3-(3,5-di-t-butyl-4-4:)'roxyphenyl)propionyloxymethylcomethane onto a smooth solid surface and solidify by cooling. A method for producing tetrakis[3-(3,5-di-butyl-4-hydroxyphenyl)propionyloxymethylcomethane] having a spherical or hemispherical gamma crystal structure, characterized by the following. (3) The manufacturing method according to claim 2, wherein the smooth solid surface is a metal plate surface. (4) Dispense the melt of tetrakis[3-(3,5-di[-butyl-4-hydroxyphenyl)propionyloxymethylcomethane] dropwise into an inert gas, cool it,
A method for producing tetrakis[:3-(3,5-di[-butyl-4-hydroxyphenyl)propionyloxymethylcomethane] having a spherical or hemispherical γ-crystal structure, which is characterized by solidifying. (5) Drop the melt of tetrakis(3-(3,5-di-t-butyl-4-k=troxyphenyl)propionyloxymethylcomethane) onto the water surface or discharge it dropwise into the water. Tetrakis [
A method for producing 3-(3,5-di(-butyl-4-hydroxyphenyl)propionyloxymethylcomethane).